Vibrational-mechanical properties of the highly-mismatched Cd1-xBexTe semiconductor alloy: experiment and ab initio calculations.

The emerging CdTe-BeTe semiconductor alloy that exhibits a dramatic mismatch in bond covalency and bond stiffness clarifying its vibrational-mechanical properties is used as a benchmark to test the limits of the percolation model (PM) worked out to explain the complex Raman spectra of the related but less contrasted Zn1-xBex-chalcogenides. The test is done by way of experiment ([Formula: see text]), combining Raman scattering with X-ray diffraction at high pressure, and ab initio calculations ([Formula: see text] ~ 0-0.5; [Formula: see text]~1). The (macroscopic) bulk modulus [Formula: see text] drops below the CdTe value on minor Be incorporation, at variance with a linear [Formula: see text] versus [Formula: see text] increase predicted ab initio, thus hinting at large anharmonic effects in the real crystal. Yet, no anomaly occurs at the (microscopic) bond scale as the regular bimodal PM-type Raman signal predicted ab initio for Be-Te in minority ([Formula: see text]~0, 0.5) is barely detected experimentally. At large Be content ([Formula: see text]~1), the same bimodal signal relaxes all the way down to inversion, an unprecedented case. However, specific pressure dependencies of the regular ([Formula: see text]~0, 0.5) and inverted ([Formula: see text]~1) Be-Te Raman doublets are in line with the predictions of the PM. Hence, the PM applies as such to Cd1-xBexTe without further refinement, albeit in a "relaxed" form. This enhances the model's validity as a generic descriptor of phonons in alloys.

Compressibility and Structural Transformations of Aluminogermanate Imogolite Nanotubes under Hydrostatic Pressure.

We present in situ pressure experiments on aluminogermanate nanotubes studied by X-ray scattering and absorption spectroscopy measurements. Structural transformations under hydrostatic pressure below 10 GPa are investigated as a function of the morphology, organization, or functionalization of the nanotubes. Radial deformations, ovalization for isolated nanotubes, and hexagonalization when they are bundled are evidenced. Radial collapse of single-walled nanotubes is shown to occur, in contrast to the double-walled nanotubes. The effect of the transmitting pressure medium used on the collapse onset pressure value is demonstrated. Axial Young's moduli are determined for isolated (400 GPa) and bundled (600 GPa) single-walled nanotubes, double-walled nanotubes (440 GPa), and methylated single-walled nanotubes (200 GPa).

Exceptionally robust magnetism and structure of SrFeO[Formula: see text] above 100 GPa.

We report the exceptional structural and magnetic stability of SrFeO[Formula: see text] under pressure by X-Ray Magnetic Circular Dichroism (XMCD) and X-ray Diffraction (XRD) up to the Mbar range. The XMCD data confirm the onset of ferromagnetism above 30 GPa and its stability up to 102 GPa while XRD shows that SrFeO[Formula: see text] structure remains unchanged from 30 GPa up to 111 GPa without any sign of structural transition. Our results demonstrate the robustness of Fe properties under extreme conditions in the square planar environment.

Exceptional phonon point versus free phonon coupling in Zn1-xBexTe under pressure: an experimental and ab initio Raman study.

Raman scattering and ab initio Raman/phonon calculations, supported by X-ray diffraction, are combined to study the vibrational properties of Zn1-xBexTe under pressure. The dependence of the Be-Te (distinct) and Zn-Te (compact) Raman doublets that distinguish between Be- and Zn-like environments is examined within the percolation model with special attention to x ~ (0,1). The Be-like environment hardens faster than the Zn-like one under pressure, resulting in the two sub-modes per doublet getting closer and mechanically coupled. When a bond is so dominant that it forms a matrix-like continuum, its two submodes freely couple on crossing at the resonance, with an effective transfer of oscillator strength. Post resonance the two submodes stabilize into an inverted doublet shifted in block under pressure. When a bond achieves lower content and merely self-connects via (finite/infinite) treelike chains, the coupling is undermined by overdamping of the in-chain stretching until a «phonon exceptional point¼ is reached at the resonance. Only the out-of-chain vibrations «survive¼ the resonance, the in-chain ones are «killed¼. This picture is not bond-related, and hence presumably generic to mixed crystals of the closing-type under pressure (dominant over the opening-type), indicating a key role of the mesostructure in the pressure dependence of phonons in mixed crystals.

Structural Metastability and Quantum Confinement in Zn1-xCoxO Nanoparticles.

This paper investigates the electronic structure of wurtzite (W) and rock-salt (RS) Zn1-xCoxO nanoparticles (NPs) by means of optical measurements under pressure (up to 25 GPa), X-ray absorption, and transmission electron microscopy. W-NPs were chemically synthesized at ambient conditions and RS-NPs were obtained by pressure-induced transformation of W-NPs. In contrast to the abrupt phase transition in W-Zn1-xCoxO as thin film or single crystal, occurring sharply at about 9 GPa, spectroscopic signatures of tetrahedral Co(2+) are observed in NPs from ambient pressure to about 17 GPa. Above this pressure, several changes in the absorption spectrum reveal a gradual and irreversible W-to-RS phase transition: (i) the fundamental band-to-band edge shifts to higher photon energies; (ii) the charge-transfer absorption band virtually disappears (or overlaps the fundamental edge); and (iii) the intensity of the crystal-field absorption peaks of Co(2+) around 2 eV decreases by an order of magnitude and shifts to 2.5 eV. After incomplete phase transition pressure cycles, the absorption edge of nontransformed W-NPs at ambient pressure exhibits a blue shift of 0.22 eV. This extra shift is interpreted in terms of quantum confinement effects. The observed gradual phase transition and metastability are related to the NP size distribution: the larger the NP, the lower the W-to-RS transition pressure.

Short-range order of compressed amorphous GeSe2.

The structure of amorphous GeSe2 (a-GeSe2) has been studied by means of a combination of two-edges X-ray absorption spectroscopy (XAS) and angle-dispersive X-ray diffraction under pressures up to about 30 GPa. Multiple-edge XAS data-analysis of a-GeSe2 at ambient conditions allowed us to reconstruct and compare the first-neighbor distribution function with previous results obtained by neutron diffraction with isotopic substitution. GeSe2 is found to remain amorphous up to the highest pressures attained, and a reversible 1.5 eV red-shift of the Ge K-edge energy indicating metallization, occurs between 10 GPa and 15 GPa. Two compression stages are identified by XAS structure refinement. First, a decrease of the first-neighbor distances up to about 10 GPa, in the same pressure region of a previously observed breakdown of the intermediate-range order. Second, an increase of the Ge-Se distances, bond disorder, and of the coordination number. This stage is related to a reversible non-isostructural transition involving a gradual conversion from tetra- to octa-hedral geometry which is not yet fully completed at 30 GPa.

Study of the invar effect through ultrasonic measurements of the elastic properties of Fe(64)Ni(36) under pressure.

The elastic properties of a polycrystalline sample of invar Fe(64)Ni(36) have been investigated at ambient temperature by ultrasonic experiments up to 7 GPa. The pressure dependence of the bulk modulus is extracted without using any model and discussed in terms of invar anomaly models.